Atomistic structures and dynamics of prenucleation clusters in MOF-2 and MOF-5 syntheses.

Chemical reactions in solution almost always take place via a series of minute intermediates that are often in rapid equilibrium with each other, and hence hardly characterizable at the level of atomistic molecular structures. We found that single-molecule atomic-resolution real-time electron microscopic (SMART-EM) video imaging provides a unique methodology for capturing and analyzing the minute reaction intermediates, as illustrated here for single prenucleation clusters (PNCs) in the reaction mixture of metal-organic frameworks (MOFs). Specifically, we found two different types of PNCs are involved in the formation of MOF-2 and MOF-5 from a mixture of zinc nitrate and benzene dicarboxylates at 95 °C and 120 °C, respectively. SMART-EM identified a small amount of 1-nm-sized cube and cube-like PNCs in the MOF-5 synthesis, but not in the MOF-2 synthesis. In the latter, we instead found only linear and square PNCs, suggesting that the MOF-2/-5 bifurcation takes place at the PNC stage.

An Amine Group Transfer Reaction Driven by Aromaticity.

A stereoselective domino inverse electron-demand Diels-Alder/amine group transfer reaction catalyzed by a bidentate Lewis acid provides 1-amino-1,2-dihydronaphthalenes, a core structure in many bioactive compounds. A concerted mechanism is proposed based on experimental studies as well as DFT computations demonstrating a new general reactivity scheme. The broad scope of the reaction was evaluated by variation of all three starting compounds, phthalazines, aldehydes, and amines. Scalability was demonstrated by a gram scale reaction without diminished yield.

Direct Microscopic Analysis of Individual C60 Dimerization Events: Kinetics and Mechanisms.

Modern transition state theory states that the statistical behavior of a chemical reaction is the sum of individual chemical events that occur randomly. Statistical analysis of each event for individual molecules in a three-dimensional space however is practically impossible. We report here that kinetics and mechanisms of chemical reactions can be investigated by using a one-dimensional system where reaction events can be observed in situ and counted one by one using variable-temperature (VT) atomic-resolution transmission electron microscopy (TEM). We thereby provide direct proof that the ensemble behavior of random events conforms to the Rice-Ramsperger-Kassel-Marcus theory, as illustrated for [2 + 2] cycloaddition of C60 molecules in carbon nanotubes (CNTs). This method gives kinetic and structural information for different types of reactions occurring simultaneously in the microscopic view field, suggesting that the VT-TEM opens a new dimension of chemical kinetics research on molecules and their assemblies in their excited and ionized states. The study carried out at 393-493 K showed that pristine CNT primarily acts as a singlet sensitizer of the cycloaddition reaction that takes place with an activation energy of 33.5 ± 6.8 kJ/mol. On the other hand, CNT suffers electron damage of the conjugated system at 103-203 K and promotes a reactive radical cation path that takes place with an activation energy of only 1.9 ± 0.7 kJ/mol. The pre-exponential factor of the Arrhenius plot gave us further mechanistic insights.

Ultrafast Excited-State Deactivation Dynamics of Cyclotrisazobenzene-A Novel Type of UV-B Absorber.

Azobenzenes are widely utilized as molecular photoswitches for control of nanoscale processes. Their photoisomerization reaction is highly robust and is retained even in extremely rigid systems. Currently, it is not clear what geometric restrictions are required to block this isomerization successfully. We present here a combined experimental and theoretical study on the ultrafast dynamics of cyclotrisazobenzene (CTA) and demonstrate that the structural constraints in CTA prevent isomerization of the photoswitch units. In the developed molecular picture, the N=N bonds respond elastically to the motion along the isomerization coordinates, which leads to ultrafast and complete dissipation of the UV excitation as heat. Based on this property, CTA and possibly other similarly designed molecules can be utilized as UV absorbers, for example in sunscreens; other potential applications are also envisioned.

Bis-Boron Compounds in Catalysis: Bidentate and Bifunctional Activation.

The development of metal-free catalysts as an alternative to the use of transition metals has gained tremendous interest in the past. In catalysis, Lewis acidity is one of the major principles used for the activation of organic compounds. Improving the reactivity and selectivity of Lewis acids by utilizing bidentate interactions was already proposed 50 years ago. Nevertheless, product inhibition due to strong binding has made applications of bidentate Lewis acids challenging for many years. Recently, bis-boron compounds have been found to be very effective and several applications in Diels-Alder reactions, carbon dioxide reduction, and ammonia-borane dehydrogenation were reported. All three transformations are enabled by the catalyst at different stages during the course of the reaction. These new and useful examples illustrate the great potential of the concept.

Bidentate Lewis Acid Catalyzed Domino Diels-Alder Reaction of Phthalazine for the Synthesis of Bridged Oligocyclic Tetrahydronaphthalenes.

A domino process consisting of an inverse and a normal electron-demand Diels-Alder reaction is presented for the formation of bridged tri- and tetracyclic 1,2,3,4-tetrahydronaphthalenes catalyzed by a bidentate Lewis acid. The products were synthesized in a one-pot reaction from commercially available starting materials and contain up to six stereogenic centers. The tetrahydronaphthalenes were isolated as single diastereomers and are derivatives of phenylethylamine, which is well-known as a scaffold of amphetamine or dopamine.

Connectivity matters - ultrafast isomerization dynamics of bisazobenzene photoswitches.

We have investigated the ultrafast dynamics of o-, m- and p-bisazobenzenes, which represent elementary building blocks for photoswitchable multiazobenzene nanostructures. The connectivity pattern within bisazobenzenes and the ensuing complex interactions between the individual azobenzene units determines the ultrafast dynamics of these compounds and their photochemical properties. While retaining a relatively high E → Z isomerization quantum yield, o-bisazobenzene exhibits a very high thermal relaxation rate (half-life of 1.6 ms). Our theoretical calculations reveal that the geometry allows intramolecular excitonic interaction between the azobenzene units, which is reflected in the femtosecond transient absorption data via the simultaneous bleaching of the two excitonic bands. In contrast, the properties of m-bisazobenzene are very similar to the monomeric azobenzene, with the two units acting nearly independently from each other. The highest degree of π conjugation extending over the two azobenzene units was observed for p-bisazobenzene, which results in strong planarity of the molecule, reduced excited state lifetime and relatively low isomerization quantum yield. Multiphotochromic systems bridge the gap between molecular photoswitches and macroscopic function and thus, understanding the properties of bisazobenzenes opens the way to the design and development of new structures with extensive and versatile applications.

Metal-Free Ammonia-Borane Dehydrogenation Catalyzed by a Bis(borane) Lewis Acid.

The storage of energy in a safe and environmentally benign way is one of the main challenges of today's society. Ammonia-borane (AB=NH3 BH3 ) has been proposed as a possible candidate for the chemical storage of hydrogen. However, the efficient release of hydrogen is still an active field of research. Herein, we present a metal-free bis(borane) Lewis acid catalyst that promotes the evolution of up to 2.5 equivalents of H2 per AB molecule. The catalyst can be reused multiple times without loss of activity. The moderate temperature of 60 °C allows for controlling the supply of H2 on demand simply by heating and cooling. Mechanistic studies give preliminary insights into the kinetics and mechanism of the catalytic reaction.

Attraction or Repulsion? London Dispersion Forces Control Azobenzene Switches.

Large substituents are commonly seen as entirely repulsive through steric hindrance. Such groups have additional attractive effects arising from weak London dispersion forces between the neutral atoms. Steric interactions are recognized to have a strong influence on isomerization processes, such as in azobenzene-based molecular switches. Textbooks indicate that steric hindrance destabilizes the Z isomers. Herein, we demonstrate that increasing the bulkiness of electronically equal substituents in the meta-position decreases the thermal reaction rates from the Z to the E isomers. DFT computations revealed that attractive dispersion forces essentially lower the energy of the Z isomers.

Chemical Talking with Living Systems: Molecular Switches Steer Quorum Sensing in Bacteria.

New avenues in bacterial engineering: An azobenzene molecular switch has been incorporated into an autoinducer for quorum sensing (QS) in bacteria. The authors demonstrated that irradiation with different wavelengths of light influences the QS system thereby controlling gene expression as well as the phenotype, as exemplified by pyocyanin production.

Symmetry as a new element to control molecular switches.

The isomerization properties of an azocarbazole macrocycle in solution were investigated utilizing NMR spectroscopy with in situ irradiation in combination with DFT calculations. It was demonstrated that the position of azo units in a rigid macrocyclic system influences the photoisomerization pathway even if the initial all-E isomer is highly symmetric. Furthermore, the effect of ring strain on lowering the rates of thermal isomerization was demonstrated and a mechanism via an inversion-rotation proposed. The herein presented results and methods give new insights into the general nature of the azobenzene unit. In particular we illustrate the effect of symmetry changes due to macrocyclic arrangement on the photochemical and thermal isomerization properties, which will stimulate future development towards multinary molecular switches.

Cyclotetraazocarbazole--a multichromic molecule.

A macrocyclic cyclotetraazocarbazole was prepared. Surprisingly, during the investigation of its photochromic behavior a drastic color change from yellow to green upon irradiation in chlorinated solvents was observed, which was temperature dependent and could also be induced by acid/base addition. With these three inputs an integrated molecular logic gate including an OR, a NOT and an AND function was build.